Multitechnique characterization of oligo(ethylene glycol) functionalized gold nanoparticles

Gold nanoparticles (AuNPs) with average diameters of ∼14 and ∼40 nm, as well as flat gold coated silicon wafers, were functionalized with oligo ethylene glycol (OEG) terminated 1-undecanethiol (HS-CH₂)₁₁ self-assembled monolayers (SAMs). Both hydroxyl [(OEG)₄OH] and methoxy [(OEG)₄OMe] terminated SAMs were prepared. The AuNPs were characterized with transmission electron microscopy (TEM), time of flight secondary ion mass spectrometry (ToF-SIMS), x-ray photoelectron spectroscopy (XPS), attenuated total reflectance Fourier infrared spectroscopy (ATR-FTIR), and low-energy ion scattering (LEIS). These studies provided quantitative information about the OEG functionalized AuNPs. TEM showed the 14 nm AuNPs were more spherical and had a narrower size distribution than the 40 nm AuNPs. ToF-SIMS clearly differentiated between the two OEG SAMs based on the C₃H₇O⁺ peak attributed to the methoxy group in the OMe terminated SAMs as well as the different masses of the [Au + M]^- ion (M = mass of the thiol molecule) from each type of SAM. Overlayer/substrate ratios quantitatively determined with XPS show a greater proportion of OEG units at the surface of 40 nm AuNPs compared to the 14 nm AuNPs. ATR-FTIR suggested the C11 backbone of the two SAMs on both AuNPs are similar and crystalline, but the OEG head groups are more crystalline on the 40 nm AuNPs compared to the 14 nm AuNPs. This indicated a better ordered SAM present at the surface of the larger, more irregular particles due to greater ordering of the OEG groups. This was consistent with the XPS and LEIS results, which showed a 30% thicker SAM was formed on the 40 nm AuNPs compared to the 14 nm AuNPs. The OH or OMe functionality did not have a significant effect on the ordering and thickness of the OEG SAMs.